The glassy polymer of polystyrene (PS) enjoys a good reputation as a promising optical material; however, the inherent brittleness hinders its further applications. Conventional toughening methods are realized based on the premise of a sacrifice in transparency and stiffness. In this work, we found an unprecedented strategy to address these obstacles by combining extensional stress-induced ductility and suppressing physical aging. PS-based film with a high stiffness, long-term ductility, and excellent transparency is achieved by introducing a styrene-butadiene block copolymer into the PS matrix and subsequently annealing stretched. A nanofibrillar structure of the polybutadiene (PB) phase is formulated surrounded by a PS matrix, and thus, the elongation at break enhances from 3.1% up to 86.8%, accompanying the yield strength enhanced from 25.5 to 62.2 MPa. More significantly, compared with neat PS, these films survive from physical aging and persistent ductility over time. The morphology deformation induced by stress makes an obvious contribution to the improvement of transparency. Investigating the dynamics of chain segments indicates that the incorporation of the copolymer can restrict rearrangement and local relaxation to the PS chain. This work could pave a potential route toward high-performance PS and might be transferable to other glassy polymers with a fragile character.